CN112920305A - Polypropylene and preparation method thereof, polypropylene composition, modified polypropylene and preparation method thereof - Google Patents
Polypropylene and preparation method thereof, polypropylene composition, modified polypropylene and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention relates to the technical field of polypropylene, and discloses polypropylene and a preparation method thereof, a polypropylene composition, modified polypropylene and a preparation method thereof, wherein the polypropylene composition contains a main antioxidant, an auxiliary antioxidant, an acid scavenger, a release agent, a nucleating agent and polypropylene; relative to 100 parts by weight of the polypropylene, the content of the main antioxidant is 0.02-0.1 part by weight, the content of the auxiliary antioxidant is 0.05-0.15 part by weight, the content of the acid scavenger is 0.02-0.1 part by weight, the content of the release agent is 0.01-0.08 part by weight, and the content of the nucleating agent is 0.1-0.3 part by weight. The polypropylene provided by the invention has higher melt index and ethylene content, the modified polypropylene provided by the invention has better toughness, rigidity, transparency and heat resistance, the product performance is more excellent, and the requirement of downstream manufacturers on the production of high-quality thin-wall transparent products can be met.
Description
Technical Field
The invention relates to the technical field of polypropylene, and particularly relates to polypropylene and a preparation method thereof, a polypropylene composition, modified polypropylene and a preparation method thereof.
Background
The polypropylene is a product polymerized by taking propylene as a monomer under the action of a catalyst, has excellent mechanical properties, non-toxicity, heat resistance, easy processing and the like, and is widely applied to a plurality of fields. In recent years, the polypropylene industry at home and abroad is continuously expanded, the market competition is intensified day by day, and the homogenized polypropylene product can not meet the market demand.
With the rapid development of the China takeaway industry, the use amount of thin-wall transparent containers such as domestic disposable water cups, milk tea cups, snack boxes and the like is gradually increased, so that the total amount of the market demand for the special thin-wall injection molding transparent polypropylene material is greatly improved, and the thin-wall injection molding polypropylene becomes a new development trend as a food packaging, storage and processing material. At present, the market competition of domestic thin-wall injection-molded transparent polypropylene is fierce, products are basically in a supply-short state, and parts of the products still need to be imported, so that the thin-wall injection-molded transparent polypropylene has the risks of high price, untimely supply and the like for downstream production enterprises, and the production cost is high; moreover, the quality of products in the market is uneven, the problems of insufficient toughness, poor transparency, difficult printing and the like of domestic thin-wall injection-molded transparent products generally exist, and the performance needs to be further improved.
Therefore, the novel modified polypropylene and the preparation method thereof have important significance.
Disclosure of Invention
The invention aims to solve the problems of insufficient toughness, poor transparency, difficult printing and the like of the existing polypropylene, and provides a polypropylene and a preparation method thereof, a polypropylene composition, a modified polypropylene and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for producing polypropylene, comprising:
(1) carrying out polymerization reaction on propylene and ethylene in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen to obtain an initial product;
(2) contacting the primary product with aqueous nitrogen for removing dissolved hydrocarbons remained in the primary product and for deactivating a main catalyst and a cocatalyst remained in the primary product, thereby obtaining polypropylene;
wherein the external electron donor is tetraethoxysilane and/or n-propyltriethoxysilane.
In a second aspect, the present invention provides a polypropylene obtainable by the process according to the first aspect of the present invention, said polypropylene having a melt index of 55 to 85g/10min under a load of 2.16kg and at 230 ℃, said polypropylene having an ethylene content of 2.5 to 4.5 wt%.
The third aspect of the present invention provides a polypropylene composition, which comprises a primary antioxidant, a secondary antioxidant, an acid scavenger, a mold release agent, a nucleating agent and the polypropylene of the second aspect of the present invention;
relative to 100 parts by weight of the polypropylene, the content of the main antioxidant is 0.02-0.1 part by weight, the content of the auxiliary antioxidant is 0.05-0.15 part by weight, the content of the acid scavenger is 0.02-0.1 part by weight, the content of the release agent is 0.01-0.08 part by weight, and the content of the nucleating agent is 0.1-0.3 part by weight.
In a fourth aspect, the present invention provides a method for preparing a modified polypropylene, which comprises the following steps: mixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger, a mold release agent and a nucleating agent and molding.
A fifth aspect of the invention provides a method as set forth in the fourth aspect of the inventionThe prepared modified polypropylene has the haze of less than or equal to 15 percent and the impact strength of a simple beam notch of more than or equal to 3.3KJ/m2The glossiness is more than 108, the bending modulus is more than or equal to 900MPa, the tensile yield stress is more than or equal to 24MPa, the crystallization temperature is more than 117 ℃, and the melting point is more than 147 ℃.
Through the technical scheme, the polypropylene provided by the invention has higher melt index and ethylene content, and the modified polypropylene provided by the invention has lower haze and higher glossiness, so that the transparency is obviously better; the impact strength of a simply supported beam notch is higher, and the bending modulus and the tensile yield stress are higher, so that the toughness is obviously better; meanwhile, the composite material has better rigidity and processability, and is suitable for producing products with high strength and high transparency; has higher crystallization temperature and melting point, thus having better heat resistance and better overall performance of the product.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a method for producing polypropylene, comprising:
(1) carrying out polymerization reaction on propylene and ethylene in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen to obtain an initial product;
(2) contacting the primary product with aqueous nitrogen for removing dissolved hydrocarbons remained in the primary product and for deactivating a main catalyst and a cocatalyst remained in the primary product, thereby obtaining polypropylene;
wherein the external electron donor is tetraethoxysilane and/or n-propyltriethoxysilane.
The preparation method of the polypropylene can be summarized as that propylene and ethylene are subjected to primary polymerization reaction in the presence of a main catalyst, a cocatalyst, hydrogen and a specific external electron donor of tetraethoxysilane and/or n-propyltriethoxysilane, and then an initial product obtained by polymerization is subjected to removal of dissolved hydrocarbon and deactivation treatment of the catalyst. In the prior art, diisobutyldimethoxysilane is generally used as an external electron donor. Compared with the traditional diisobutyldimethoxysilane (DIBDMS), the invention can realize low hydrogen consumption by using Tetraethoxysilane (TEOS) and/or n-propyltriethoxysilane, so that polypropylene products with higher melt index can be produced under the same hydrogen concentration.
In some embodiments of the present invention, the addition amount of ethylene and hydrogen can be controlled to make the prepared polypropylene product have higher melt index and ethylene content, preferably, the molar ratio of ethylene to propylene in step (1) is 0.03-0.1: 1, more preferably 0.03 to 0.05: 1.
preferably, the molar ratio of hydrogen to propylene is from 0.02 to 0.04: 1, more preferably 0.02 to 0.025: 1.
preferably, the mass ratio of the main catalyst to the propylene is 0.00011-0.00017: 1. in the present invention, the mass ratio of the main catalyst to propylene represents the ratio of the main catalyst to the feed amount of propylene per hour.
In some embodiments of the present invention, two parameters, Al/Mg molar ratio and Al/Si molar ratio, are used to control the amount of cocatalyst and external electron donor added, thereby controlling the product characteristics. Namely the addition amount of the cocatalyst is controlled by the addition amount of the main catalyst, and the addition amount of the external electron donor is controlled by the addition amount of the cocatalyst, preferably, in the step (1), the molar ratio of aluminum in the cocatalyst to magnesium in the main catalyst, namely the molar ratio of Al/Mg is 4-6: 1.
in some embodiments of the present invention, preferably, in step (1), the molar ratio of aluminum in the cocatalyst to silicon in the external electron donor, i.e. the Al/Si molar ratio, is 4-12: 1.
the selection range of the main catalyst in the step (1) is wide, and the main catalyst is preferably selectedThe agent comprises TiCl4、MgCl2And supported on MgCl2Di-n-butyl phthalate. For example, the main catalyst may be selected from the group consisting of a CD/CDI catalyst from Amoco or a SAL catalyst from hokyo oda catalyst, and further preferably, the main catalyst is selected from the group consisting of a SAL catalyst from hokyo oda catalyst. The SAL catalyst of the present invention comprises 2 to 3.2 wt% titanium, 17.6 to 20.6 wt% magnesium, 50 to 62 wt% chlorine and 6 to 18 wt% ester.
The selection range of the cocatalyst in step (1) in the present invention is wide, and preferably, the cocatalyst is an alkyl aluminum compound, more preferably at least one selected from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum, and further preferably triethyl aluminum.
In some embodiments of the present invention, preferably, in step (1), the polymerization conditions include: the temperature is 60-80 ℃, and the pressure is 2.1-2.5 MPa.
According to the invention, in step (2) the initial product obtained in step (1) is contacted with aqueous nitrogen, which on the one hand acts as a stripping gas and enables the dissolved hydrocarbons to be removed from the initial product; on the other hand, the aqueous nitrogen gas can react with the main catalyst and the cocatalyst which remain in the primary product to deactivate them. In the present invention, the dissolved hydrocarbons are propane and ethane in low concentrations.
The water content in the aqueous nitrogen gas and the contacting conditions in the step (2) are not particularly limited in the present invention, and may be selected conventionally in the art as long as the dissolved hydrocarbons remaining in the primary product can be removed and the catalyst is subjected to a deactivation treatment.
The polymerization reactor used for carrying out the polymerization reaction in the present invention is not particularly limited and may be conventionally selected in the art, and preferably, the polymerization reactor is a horizontal stirred bed reactor.
In the present invention, the level of the polymerization reactor is critical to the system stability production of propylene polymerization, and preferably, the level of the polymerization reactor is 70 to 75%, wherein the level indicates the position of the material.
In order to clearly describe the process for preparing the polypropylene according to the present invention, a preferred embodiment is provided below for illustration:
(1) in a horizontal stirred bed reactor, in the presence of a main catalyst (comprising TiCl)4、MgCl2And supported on MgCl2In the presence of di-n-butyl phthalate), a cocatalyst (triethylaluminum), an external electron donor (tetraethoxysilane and/or n-propyltriethoxysilane) and hydrogen, carrying out polymerization reaction on propylene and ethylene at the temperature of 60-80 ℃ and the pressure of 2.1-2.5MPa to obtain a primary product, wherein the material level of the reactor is 70-75%, and the molar ratio of ethylene to propylene is 0.03-0.05: 1, the molar ratio of hydrogen to propylene is from 0.02 to 0.025: 1, the mass ratio of the main catalyst to the propylene is 0.00011-0.00017: 1, the molar ratio of Al to Mg is 4-6: 1, Al/Si molar ratio of 4-12: 1;
(2) the primary product is contacted with aqueous nitrogen gas for removing low concentrations of propane and ethane remaining in the primary product and for deactivating the main catalyst and the co-catalyst remaining therein, thereby obtaining polypropylene.
By adopting the Innovene polypropylene gas-phase polymerization process, the phenomena of sticking, blocking and the like in the production process can be effectively controlled, the process production process is controllable, the production stability is high, and the large-scale periodic production of polypropylene products can be realized.
The second aspect of the present invention provides a polypropylene obtainable by the process as described above, said polypropylene having a melt index at 230 ℃ under a load of 2.16kg of from 55 to 85g/10min and an ethylene content of from 2.5 to 4.5 wt%. The polypropylene prepared by the method has higher melt index and ethylene content, so that the polypropylene has better fluidity and toughness.
According to a preferred embodiment of the present invention, the polypropylene has a melt index of 70 to 80g/10min under a load of 2.16kg and at 230 ℃ and the content of ethylene in the polypropylene is 2.8 to 3.5 wt.%.
In a third aspect, the present invention provides a polypropylene composition, which contains a primary antioxidant, a secondary antioxidant, an acid scavenger, a mold release agent, a nucleating agent, and the polypropylene provided by the present invention;
relative to 100 parts by weight of the polypropylene, the content of the main antioxidant is 0.02-0.1 part by weight, the content of the auxiliary antioxidant is 0.05-0.15 part by weight, the content of the acid scavenger is 0.02-0.1 part by weight, the content of the release agent is 0.01-0.08 part by weight, and the content of the nucleating agent is 0.1-0.3 part by weight.
According to a preferred embodiment of the present invention, the primary antioxidant is contained in an amount of 0.03 to 0.08 parts by weight, the secondary antioxidant is contained in an amount of 0.06 to 0.13 parts by weight, the acid scavenger is contained in an amount of 0.03 to 0.08 parts by weight, the mold release agent is contained in an amount of 0.02 to 0.06 parts by weight, and the nucleating agent is contained in an amount of 0.15 to 0.25 parts by weight, based on 100 parts by weight of the polypropylene;
according to a more preferred embodiment of the present invention, the primary antioxidant is contained in an amount of 0.04 to 0.06 parts by weight, the secondary antioxidant is contained in an amount of 0.08 to 0.12 parts by weight, the acid scavenger is contained in an amount of 0.04 to 0.06 parts by weight, the mold release agent is contained in an amount of 0.03 to 0.05 parts by weight, and the nucleating agent is contained in an amount of 0.18 to 0.22 parts by weight, based on 100 parts by weight of the polypropylene. The modified polypropylene which meets the content of the specific components has better transparency, toughness, rigidity and heat resistance, and the overall performance is more excellent.
In some embodiments of the present invention, the primary antioxidant is a stabilizer for processing, which captures alkoxy radicals and peroxy radicals to prevent oxidative degradation of polypropylene during processing, and the primary antioxidant is selected from a wide range of primary antioxidants, preferably, the primary antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) and/or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (antioxidant 3114), more preferably pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
In some embodiments of the present invention, the secondary antioxidant is selected from a wide range, preferably, the secondary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626), more preferably tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168). The auxiliary antioxidant is a heat stabilizer and mainly plays a role in decomposing peroxide, catalyst residues and reducing quinone compounds.
In some embodiments of the present invention, the acid scavenger is selected from a wide range, preferably, the acid scavenger is selected from at least one of calcium stearate, hydrotalcite, and zinc oxide, more preferably calcium stearate. The acid scavenger is mainly used for absorbing residual halogen such as chlorine in polypropylene and reducing the influence of acidic substances on the corrosion of processing equipment and the color of products.
In some embodiments of the present invention, the selection of the release agent is wide, and preferably, the release agent is the release agent GMS90 and/or the release agent GMS60, more preferably, the release agent GMS 90. The release agent has an antistatic effect, is small in molecular weight, has a polar head with a proper size, is easy to migrate to the surface of polypropylene to play an antistatic role, and can play a good releasing role in the process of injection molding products, so that the thin-wall injection molding modified polypropylene products can be separated from a mold more easily.
In some embodiments of the present invention, the nucleating agent is selected from a wide range, preferably the nucleating agent is bis-1, 3-2,4- (4 '-propylbenzylidene) -1-propyl sorbitol (nucleating agent NX8000) and/or bis (3, 4-dimethylbenzylidene) sorbitol (nucleating agent 3988), more preferably bis-1, 3-2,4- (4' -propylbenzylidene) -1-propyl sorbitol (nucleating agent NX 8000). In this preferable case, a modified polypropylene product having better transparency can be produced. The nucleating agent is used for improving the light transmission performance of a polymer and increasing the rigidity of a product, the existing modified polypropylene product generally has the defect of poor transparency, and the nucleating agent can be added to obviously improve the transparency and the glossiness of the modified polypropylene product, simultaneously ensure that the crystallization temperature of a melt is higher, the molding period is shorter and the productivity is improved.
The fourth aspect of the present invention provides a method for preparing modified polypropylene, which is prepared from the components of the polypropylene composition provided above, and comprises: mixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger, a mold release agent and a nucleating agent and molding. The modified polypropylene obtained by mixing and molding the polypropylene with high melt index and ethylene content with other additives comprising a main antioxidant, an auxiliary antioxidant, an acid scavenger, a mold release agent and a nucleating agent according to a specific dosage ratio has better product performance.
In some embodiments of the present invention, the molding method is not particularly limited, and extrusion molding is preferable. The extruder to be used for the extrusion molding in the present invention is not particularly limited and may be conventionally selected in the art, and preferably, the extruder is a CMP387 twin-screw extrusion pelletizer manufactured by JSW of japan, and the load is up to 70 tons/hour.
In some embodiments of the present invention, because the flowability of the thin-wall injection molding modified polypropylene product is very strong, the extruder is easy to wind a cutter and stop, and in order to obtain a better granulation effect, the temperature of the die plate and the temperature of the barrel of the extruder are reduced during the production process, so that a better granulation effect can be achieved, preferably, the extrusion molding conditions include: the temperature of the template is 230-250 ℃, the temperature of the extrusion cylinder is 200-230 ℃, and the temperature of the cooling water is 40-60 ℃. Wherein, the temperature of the extrusion cylinder body means that the temperature of each section (including one section to seven sections) in the extrusion cylinder body is respectively 200-230 ℃.
In order to clearly describe the preparation method of the modified polypropylene of the present invention, a preferred embodiment is provided below for illustration:
the modified polypropylene is prepared by uniformly mixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger, a release agent and a nucleating agent according to the following proportion that the content of the main antioxidant is 0.04-0.06 part by weight, the content of the auxiliary antioxidant is 0.08-0.12 part by weight, the content of the acid scavenger is 0.04-0.06 part by weight, the content of the release agent is 0.03-0.05 part by weight and the content of the nucleating agent is 0.18-0.22 part by weight, and extruding and molding the mixture by an extruder under the conditions that the template temperature is 230-250 ℃, the temperature of each section of an extrusion cylinder is 200-230 ℃ and the cooling water temperature is 40-60 ℃.
The fifth aspect of the invention provides modified polypropylene prepared by the method, wherein the haze of the modified polypropylene is less than or equal to 15%, and the impact strength of a simple beam notch is more than or equal to 3.3KJ/m2The glossiness is more than 108, the bending modulus is more than or equal to 900MPa, the tensile yield stress is more than or equal to 24MPa, the crystallization temperature is more than 117 ℃, and the melting point is more than 147 ℃. The modified polypropylene meeting the performance indexes has good transparency, toughness, rigidity and heat resistance.
According to a preferred embodiment of the invention, the modified polypropylene has a haze of 10-12% and a simple beam notched impact strength of 3.8-4.2KJ/m2The glossiness is 110-120, the bending modulus is 1000-1100MPa, the tensile yield stress is 28-30MPa, the crystallization temperature is 121-125 ℃, and the melting point is 150-155 ℃. In this preferable case, the modified polypropylene has better transparency, toughness, rigidity and heat resistance.
The pressures described herein are all expressed as gauge pressures unless otherwise specified.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Main catalyst: SAL catalyst, available from okada catalyst, beijing;
and (3) a cocatalyst: triethylaluminum, available from chekiang foreeder chemical ltd;
external electron donor: tetraethoxysilane, available from Huabang chemical Co., Ltd, Hubei;
the melt index of the polypropylene is tested by referring to GB/T3682-2018 (230 ℃, 2.16kg load);
the content of ethylene in the polypropylene is tested by adopting a Fourier infrared spectroscopy;
the haze of the modified polypropylene is tested according to GB/T2410-2008;
the gloss of the modified polypropylene was tested with reference to GB 8807-1988;
the flexural modulus of the modified polypropylene is tested according to GB/T9341;
the tensile yield stress of the modified polypropylene is tested according to GB/T1040.2;
the crystallization temperature and the melting point of the modified polypropylene are tested according to GB/T19466.3-2004;
the notch impact strength of the simply supported beam of the modified polypropylene is tested according to GB/T1043.1-2008.
Preparation of Polypropylene
Preparation example 1
(1) In a horizontal stirred bed reactor, in the presence of SAL catalyst, triethylaluminum, tetraethoxysilane and hydrogen, propylene and ethylene are subjected to polymerization reaction at the temperature of 60 ℃ and the pressure of 2.1MPa to obtain a primary product, wherein the material level of the reactor is 70%, the feeding amount of propylene is 30t/h, the feeding amount of the SAL catalyst is 4kg/h, and the molar ratio of ethylene to propylene is 0.03: 1, the molar ratio of hydrogen to propylene is 0.021: 1, the molar ratio of Al in triethylaluminum to Mg in SAL catalyst, i.e. Al/Mg, is 4: 1, the molar ratio of Al in triethylaluminum to Si in tetraethoxysilane, i.e. Al/Si, is 4: 1;
(2) the initial product was contacted with aqueous nitrogen for removing low concentrations of propane, ethane remaining in the initial product and for deactivating the SAL catalyst and triethylaluminium remaining therein to give polypropylene a1 having the performance parameters listed in table 1.
Preparation example 2
(1) In a horizontal stirred bed reactor, in the presence of an SAL catalyst, triethylaluminum, n-propyltriethoxysilane and hydrogen, propylene and ethylene are subjected to polymerization reaction at the temperature of 70 ℃ and the pressure of 2.2MPa to obtain a primary product, wherein the material level of the reactor is 75%, the feeding amount of propylene is 32t/h, the feeding amount of the SAL catalyst is 4.1kg/h, and the molar ratio of ethylene to propylene is 0.035: 1, molar ratio of hydrogen to propylene of 0.023: 1, the molar ratio of Al in triethylaluminum to Mg in SAL catalyst, i.e. Al/Mg, is 6: 1, the molar ratio of Al in triethyl aluminum to Si in n-propyltriethoxysilane, i.e. the Al/Si molar ratio, is 12: 1;
(2) the initial product was contacted with aqueous nitrogen gas for removing low concentrations of propane and ethane remaining in the initial product and for deactivating the main catalyst and the co-catalyst remaining therein to obtain polypropylene a2, the performance parameters of which are shown in table 1.
Preparation example 3
(1) In a horizontal stirred bed reactor, propylene and ethylene are subjected to polymerization reaction at the temperature of 65 ℃ and the pressure of 2.15MPa in the presence of SAL catalyst, triethylaluminum, tetraethoxysilane and hydrogen to obtain a primary product, wherein the material level of the reactor is 73 percent, the feeding amount of the propylene is 34t/h, the feeding amount of the SAL catalyst is 4.3kg/h, and the molar ratio of the ethylene to the propylene is 0.04: 1, molar ratio of hydrogen to propylene of 0.024: 1, the molar ratio of Al in triethylaluminum to Mg in SAL catalyst, i.e. Al/Mg, is 5: 1, the molar ratio of Al in triethylaluminum to Si in tetraethoxysilane, i.e. Al/Si, is 8: 1;
(2) the initial product was contacted with aqueous nitrogen gas for removing low concentrations of propane and ethane remaining in the initial product and for deactivating the main catalyst and the co-catalyst remaining therein to obtain polypropylene a3, the performance parameters of which are shown in table 1.
Preparation example 4
The procedure of example 1 was followed except that, in the step (1), the molar ratio of ethylene to propylene was changed to 0.1: 1, thus obtaining polypropylene a4, the performance parameters of which are listed in table 1.
Preparation example 5
The process of example 1 was followed except that in step (1), the molar ratio of hydrogen to propylene was changed to 0.04: 1, thus obtaining polypropylene a5, the performance parameters of which are listed in table 1.
Comparative preparation example 1
The procedure of preparation 1 was followed, except that tetraethoxysilane was replaced with diisobutyldimethoxysilane, to obtain polypropylene DA1, the performance parameters of which are shown in Table 1.
TABLE 1
| Sample numbering | Melt index (g/10min) | Ethylene content (%) |
| A1 | 70 | 3.0 |
| A2 | 75 | 3.2 |
| A3 | 77 | 3.4 |
| A4 | 71 | 4.2 |
| A5 | 83 | 2.9 |
| DA1 | 32 | 2.2 |
Note: the melt index represents the melt index of polypropylene under a load of 2.16kg and at 230 ℃;
the ethylene content represents the ethylene content of the polypropylene.
As can be seen from the results in Table 1, compared with the polypropylene prepared by the prior art, the polypropylene product prepared by the invention has higher melt index and ethylene content by adopting tetraethoxysilane and/or n-propyltriethoxysilane with better hydrogen regulation sensitivity as an external electron donor.
Example 1
The polypropylene composition formulations are listed in table 2.
The polypropylene prepared by the preparation example, the main antioxidant, the auxiliary antioxidant, the acid scavenger, the release agent and the nucleating agent are uniformly mixed, and are extruded and molded by an extruder under the conditions that the temperature of a template is 230 ℃, the temperature of each section of an extrusion cylinder is 200 ℃, 210 ℃ and the temperature of cooling water is 40 ℃ respectively, so as to obtain the modified polypropylene.
The polypropylene composition formulations of the other examples and comparative examples are shown in Table 2.
TABLE 2
Table 2 (continuation watch)
Table 2 (continuation watch)
Table 2 (continuation watch)
Table 2 (continuation watch)
Table 2 (continuation watch)
Note: "-" indicates that the component is not contained.
Test example 1
The test examples were used for evaluating the properties of the modified polypropylenes prepared in the above examples and comparative examples, and the evaluation results are shown in Table 3.
TABLE 3
| B1 | B2 | B3 | B4 | B5 | |
| Haze (%) | 10.2 | 11.1 | 10.8 | 13.1 | 13.8 |
| Degree of gloss | 118 | 117 | 119 | 115 | 111 |
| Impact strength of simply supported beam notch (KJ/m)2) | 4.0 | 4.1 | 3.9 | 3.4 | 3.8 |
| Flexural modulus (MPa) | 1089 | 1087 | 1093 | 1011 | 1003 |
| Tensile yield stress (MPa) | 28.3 | 29.0 | 28.7 | 24.5 | 25.4 |
| Crystallization temperature (. degree.C.) | 121.8 | 123.2 | 121.6 | 118.2 | 120.4 |
| Melting Point (. degree.C.) | 153.8 | 155.0 | 152.3 | 147.2 | 148.1 |
Table 3 (continuation watch)
| B6 | B7 | B8 | B9 | B10 | |
| Haze (%) | 14.9 | 14.1 | 14.6 | 14.8 | 14.3 |
| Degree of gloss | 109 | 110 | 112 | 113 | 115 |
| Impact strength of simply supported beam notch (KJ/m)2) | 3.3 | 3.9 | 3.7 | 3.8 | 3.5 |
| Flexural modulus (MPa) | 1010 | 1046 | 1005 | 992 | 990 |
| Tensile yield stress (MPa) | 25.6 | 25.8 | 25.3 | 24.8 | 25.1 |
| Crystallization temperature (. degree.C.) | 120.4 | 120.9 | 119.1 | 121.1 | 119.2 |
| Melting Point (. degree.C.) | 148.0 | 149.1 | 148.4 | 148.3 | 148.2 |
Table 3 (continuation watch)
| B11 | B12 | B13 | B14 | B15 | |
| Haze (%) | 12.5 | 13.6 | 12.6 | 14.4 | 12.8 |
| Degree of gloss | 113 | 111 | 116 | 110 | 116 |
| Impact strength of simply supported beam notch (KJ/m)2) | 4.0 | 3.8 | 3.9 | 3.7 | 3.9 |
| Flexural modulus (MPa) | 1011 | 1002 | 1068 | 1006 | 1057 |
| Tensile yield stress (MPa) | 26.5 | 25.3 | 27.0 | 25.8 | 27.5 |
| Crystallization temperature (. degree.C.) | 120.1 | 118.3 | 121.1 | 118.4 | 120.8 |
| Melting Point (. degree.C.) | 149.8 | 147.3 | 149.4 | 147.9 | 149.8 |
Table 3 (continuation watch)
Table 3 (continuation watch)
| DB1 | DB2 | DB3 | DB4 | |
| Haze (%) | 18.2 | 25.3 | 20.6 | 19.2 |
| Degree of gloss | 86 | 60.8 | 83 | 92 |
| Impact strength of simply supported beam notch (KJ/m)2) | 2.3 | 2.6 | 2.8 | 3.0 |
| Flexural modulus (MPa) | 948 | 865 | 957 | 989 |
| Tensile yield stress (MPa) | 21.9 | 18.8 | 20.9 | 22.3 |
| Crystallization temperature (. degree.C.) | 114.8 | 110.1 | 118.2 | 116.3 |
| Melting Point (. degree.C.) | 140.2 | 136.2 | 141.7 | 140.6 |
As can be seen from the results in Table 3, compared with the modified polypropylene provided by the prior art, the modified polypropylene provided by the invention has better toughness, rigidity, transparency and heat resistance by adopting the combined action of the specific components and contents, has better product performance, and can meet the requirement of downstream manufacturers on the production of high-quality thin-wall transparent products.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A process for producing polypropylene, comprising:
(1) carrying out polymerization reaction on propylene and ethylene in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen to obtain an initial product;
(2) contacting the primary product with aqueous nitrogen for removing dissolved hydrocarbons remained in the primary product and for deactivating a main catalyst and a cocatalyst remained in the primary product, thereby obtaining polypropylene;
wherein the external electron donor is tetraethoxysilane and/or n-propyltriethoxysilane.
2. The process according to claim 1, wherein in step (1), the molar ratio of ethylene to propylene is from 0.03 to 0.1: 1, preferably 0.03 to 0.05: 1;
preferably, the molar ratio of hydrogen to propylene is from 0.02 to 0.04: 1, preferably 0.02 to 0.025: 1;
preferably, the mass ratio of the main catalyst to the propylene is 0.00011-0.00017: 1.
3. the process according to claim 1 or 2, wherein in step (1), the molar ratio of the aluminum in the cocatalyst to the magnesium in the procatalyst is 4-6: 1;
preferably, the molar ratio of aluminium in the cocatalyst to silicon in the external electron donor is from 4 to 12: 1;
preferably, the procatalyst comprises TiCl4、MgCl2And supported on MgCl2Di-n-butyl phthalate.
4. The process according to any one of claims 1 to 3, wherein in step (1), the polymerization conditions comprise: the temperature is 60-80 ℃, and the pressure is 2.1-2.5 MPa.
5. The polypropylene produced by the process of any one of claims 1 to 4, wherein the polypropylene has a melt index of 55 to 85g/10min under a load of 2.16kg and at 230 ℃ and an ethylene content of 2.5 to 4.5 wt%.
6. The polypropylene according to claim 5, wherein the polypropylene has a melt index of 70 to 80g/10min under a load of 2.16kg and at 230 ℃ and an ethylene content of 2.8 to 3.5 wt%.
7. A polypropylene composition comprising a primary antioxidant, a secondary antioxidant, an acid scavenger, a mold release agent, a nucleating agent and the polypropylene of claim 5 or 6;
relative to 100 parts by weight of the polypropylene, the content of the main antioxidant is 0.02-0.1 part by weight, the content of the auxiliary antioxidant is 0.05-0.15 part by weight, the content of the acid scavenger is 0.02-0.1 part by weight, the content of the release agent is 0.01-0.08 part by weight, and the content of the nucleating agent is 0.1-0.3 part by weight.
8. The composition according to claim 7, wherein the primary antioxidant is contained in an amount of 0.03 to 0.08 parts by weight, the secondary antioxidant is contained in an amount of 0.06 to 0.13 parts by weight, the acid scavenger is contained in an amount of 0.03 to 0.08 parts by weight, the mold release agent is contained in an amount of 0.02 to 0.06 parts by weight, and the nucleating agent is contained in an amount of 0.15 to 0.25 parts by weight, relative to 100 parts by weight of the polypropylene;
more preferably, the content of the main antioxidant is 0.04-0.06 weight part, the content of the auxiliary antioxidant is 0.08-0.12 weight part, the content of the acid scavenger is 0.04-0.06 weight part, the content of the release agent is 0.03-0.05 weight part, and the content of the nucleating agent is 0.18-0.22 weight part, relative to 100 weight parts of the polypropylene.
9. The composition according to claim 7 or 8, wherein the primary antioxidant is pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, more preferably pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
preferably, the secondary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, more preferably tris (2, 4-di-tert-butylphenyl) phosphite;
preferably, the acid scavenger is selected from at least one of calcium stearate, hydrotalcite and zinc oxide, more preferably calcium stearate;
preferably, the release agent is the release agent GMS90 and/or the release agent GMS60, more preferably the release agent GMS 90;
preferably, the nucleating agent is bis-1, 3-2,4- (4 '-propylbenzylidene) -1-propylsorbitol and/or bis (3, 4-dimethylbenzylidene) sorbitol, more preferably bis-1, 3-2,4- (4' -propylbenzylidene) -1-propylsorbitol.
10. A process for the preparation of a modified polypropylene, characterized in that it is prepared from the components of a polypropylene composition according to any one of claims 7 to 9, which process comprises: mixing polypropylene, a main antioxidant, an auxiliary antioxidant, an acid scavenger, a mold release agent and a nucleating agent and molding.
11. The method of claim 10, wherein the forming is by extrusion;
preferably, the extrusion molding conditions include: the temperature of the template is 230-250 ℃, the temperature of the extrusion cylinder is 200-230 ℃, and the temperature of the cooling water is 40-60 ℃.
12. The modified polypropylene prepared by the method of claim 10 or 11, wherein the haze of the modified polypropylene is less than or equal to 15%, and the impact strength of a simple beam notch is more than or equal to 3.3KJ/m2Gloss > 108, bending dieThe amount is more than or equal to 900MPa, the tensile yield stress is more than or equal to 24MPa, the crystallization temperature is more than 117 ℃, and the melting point is more than 147 ℃.
13. The modified polypropylene of claim 12, wherein the modified polypropylene has a haze of 10 to 12% and a simple beam notched impact strength of 3.8 to 4.2KJ/m2The glossiness is 110-120, the bending modulus is 1000-1100MPa, the tensile yield stress is 28-30MPa, the crystallization temperature is 121-125 ℃, and the melting point is 150-155 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0253810A (en) * | 1988-08-18 | 1990-02-22 | Mitsui Toatsu Chem Inc | Production of olefin copolymer |
| CN103788255A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Polypropylene product and preparation method thereof |
| CN110746702A (en) * | 2019-10-30 | 2020-02-04 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN112194848A (en) * | 2020-09-25 | 2021-01-08 | 中国神华煤制油化工有限公司 | Polypropylene composition containing nucleating agent, modified polypropylene and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0253810A (en) * | 1988-08-18 | 1990-02-22 | Mitsui Toatsu Chem Inc | Production of olefin copolymer |
| CN103788255A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Polypropylene product and preparation method thereof |
| CN110746702A (en) * | 2019-10-30 | 2020-02-04 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN112194848A (en) * | 2020-09-25 | 2021-01-08 | 中国神华煤制油化工有限公司 | Polypropylene composition containing nucleating agent, modified polypropylene and preparation method thereof |
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